Production of dyestuffs and intermediates



Patented Aug. 29, 1933 UNITED STATES PRODUCTION DYESTUFFS AND 7 INTERMEDIATES David Alexander Whyte Fairweatlier and'John Thomas, Grangemouth, Scotland, assignors to Scottish Dyes Limited, Grangemouth, Scotland No Drawing. Application February 6, 1930, Serial No. 426,417, and in Great Britain February 8, 1929 This invention relates to the production of am dyestuffs and intermediates. The object of the present invention is to provide improved or modified azo dyestuiis and intermediates or improved or modified processes for making or using azo dyestufis and intermediates.

In a co-pending application corresponding to British application No. 4328/29, (Serial No. 10 423179, filed 24th January 1930) there are described processes for using certain products. The present application deals with methods for producing starting materials which may be used for the purposes or" the processes of the aforesaid copending application.

As a result of researches we have foundaniong other things that 5 amino anthraquinone disulphuric acid ester, when treated with sodium nitrite, can be converted to the diazo derivative. This is a most surprising result in View of the fact that these esters are normally oxidized and hydrolyzed by sodium nitrite in acid solution. The resulting diazo body we also find will couple with amines, phenols or the like; in fact it appears to behave justlike an ordinary diazo body.

The resulting coupled products may be used as dyestufis and for example will dye vegetable or animal fibres. By treatment with acid oxidiz- 30 ing agents the ester groups are apparently hydrolyzed and oxidized to give the azo body on the fibre.

Using this important discovery as a basis we have found that we can provide a range of products for dyeing which are not intact vat dyestuffs. The matter appears to be comprehensive, and to include for instance the diazotization of esters containing amino groups, and the coupling of the diazotized bodies with the usual azo dyestuffs components, such as amines, phenols or the like. a V I With regard to the esters, carboxylic acid esters containing amino groups as diazo components have been proposed for use in the manufacture of azo dyestuffs for a long time, but the esters used as starting materials for the processes of the present application are sulphuricesters of amino anthrahydroquinones.

We have found that coupling maybe carried out in acid, alkaline or neutral solution according to the components employed. v

The following examples illustrate how the inventicn may be carried into efifect the principal features being later indicated by the claims,

references to parts being to parts by Weight:-

'parts of sodium nitrite in aqueous solution, the

15 Claims. (01. 260-86) Example 1 429 parts of thesodium salt of beta-amino anthrahydroquinone disulphuric acid ester are dissolved in water and ice added until the temperature is at 0 C. 30 parts of hydrochloric acid of" specific gravity 1.16 are now added and the solution of the hydrochloride of beta-aminoanthrahydroquinone disulphuric acid ester so obtained diazotized by the slow addition of 6.9

temperature being kept below 5 by the addition of a further quantity of ice if necessary: The diazo anthrahydroquinone disulphuric acid ester may be'filteredofi, or'its solution or suspension may be used for further reactions without isolation p The structural formula of the product is:-- oso3H osousi I Escamplez QN=N / osoaNa Example 3 42.9 parts ofthe sodium salt of beta-amirioanthrahydroquinone disulphuric acid ester are diazotized as in Example 1 and the solution or suspension so. obtained is run slowly with stirring into an alkaline solution of 5-chlor-orthotoluidide 10 of beta-hydroxy-naphthoic .acid made from 31.5 parts of 5-chlor-orthotoluidide of beta-hydroxynaphthoic'acid and 10 parts of caustic soda as in Example 1. The mixture is stirred for one hour at ordinary temperature and then warmed and 1 the dyestufi salted out.

The structural formula of the product is:-

OSOzNa 0H OSOaNa oo-1 IH 01 Example 4 The diazonium salt prepared as in. Example 1 OSOsNa OSOiNa from 42.9 parts of the sodium salt of beta-aminoanthrahydroquinone disulphuric acid ester is introduced at 5 C. into an aqueous solution of 22 parts of the sodium salt of 1:5 amino naphthoic acid to which has been added 30 parts of sodium acetate. The mixture is stirred at 5 C. for 1 hour, and then the temperature is allowed to rise to 15 C. When the coupling is complete the mixture is warmed and the dark orange dyestufi salted out.

The structural formula of the product is:-

OSOaNa OS05N9.

Example 5 OSOaNa OSOJNa on I -01 Naois NHG O-NH The product is bluish-violet in color and is converted to orange on acid oxidation.

Example 6 If the diazo solution obtained as in Example 5 from 495 parts of the potassium salt of Z-amino- A 3-chlor-anthrahydroquinone-9:10-disu1phuric ester is similarly combined with a solution containing 252 parts of 5:5-dihydroxy-2:2-dinaphthy1- urea-7:'I-disulphonic acid in presence of 350 parts of sodium carbonate, there is obtained a brownish-violet dyestuff converted to red by acid oxidation.

The structural formula of the brownish-violet dyestuff is:-

on QSOaNa so Na or OSOzNa Example 7 I To the diazo solution obtained as described in either of the two preceding examples, using 495 parts of the ester, 300 parts of 36% hydrochloric acid and 69 parts of sodium nitrite, there is added a solution containing 239 parts of 2-amino8- naphthol-6 sulphonic acid and 250 parts of sodium acetate crystals. The mixture is stirred until combination is complete, when it is made alkaline and the dyestuff is salted out with common salt.

The structural formula of the product is:-

QSO3N8 NH:

OSOaNa some Example 8 To the diazo solution obtained from 495 parts of the potassium salt of 2-amino-3-chlor-anthrahydroquinone9zlo-disulphuric ester, 300 parts of 36% hydrochloric acid and 69 parts of sodium nitrite, there is added a solution of the hydrochloride obtained from 137 parts of meta-aminopara-cresol-methyl-ether together with 300 parts of sodium acetate crystals.

The mixture, which is free from mineral acid, is stirred until coupling is complete and is then neutralized. The resulting amino azo dyestuif is now diazotized by the addition of 69 parts of 36% hydrochloric acid and the suspension of diazo compound is then stirred into a cold solution containing 337 parts of the sodium salt of 2- phenyl-amino-5-naphthol-7-sulphonic acid and 400 parts of sodium carbonate.

After stirring the mixture, meanwhile maintaining it alkaline with sodium carbonate until couplingis complete, the dyestuff is salted out by the addition of common salt.

The structural formula of the product is:-'

OSOaNa e m N=N NaOaS NHCuH:

/ c1 N=N osolNa 00H; 0'11 Example A neutral solution of 319 parts of 1:8-aminonaphthol-326-disulphonic acid is stirred into the diazo solution obtained as already described from 495 parts of the potassium salt of 2-amino-3- chlor-anthrahydroquinone-9 lo-disulphuric ester, 300 parts of 36% hydrochloric acid and 69 parts of sodium nitrite. When coupling is complete the mixture is made neutral and 400 parts of sodium carbonate are added. There is then run in with continuous stirring a solution of benzene diazonium chloride obtained from 93 parts of aniline in the known manner. When combination is complete, the dyestuff is precipitated by the addition of common salt.

The structural formula of the product is:-

OSOaNa 171B: ()3 N I N:

Cl NaOaS SOaNa OSOaNa It is a violet body, turning to blue on acid oxi-- dation.

Example 10 OSOaNa IIIH: N=N

OSOaNa I|\'I N Example 11 This'describes the diazotization of .l-aminoanthrahydroquinone disulphuric acid ester which is carried out in the similar manner to'that' of the corresponding 2-amino-derivative 11 Example 1.

The structural formula of the product is:

osolNa N=NOl OSOsNa An example of a product obtained by coupling this will be found in the table below.

Example 12 V This is an example of the preparation of a diazo solution from Z-amino-l-chlor-anthra- -hydroquinone-disulphuric acid ester.

This preparation is carried out in the same way as is described in Example 5. no

The structural formulaof the product 5:-

QSOgNa N=N--o1 SOaNB An example of a product obtained by coupling this will be found in the table below.

V i Example 13 This is an example of the diazotization of diamino-anthrahydroquinone ester.

44.4parts of the sodium salt of 2: 6-diamino- 1'40 anthrahydroquinone+9:lO-disiilphuric acid ester are dissolved in Water andc'c'ooled to 0 C. with ice. V I

60 parts of concentrated hydrochloric acid are then added and the tetrazotization carried out with a solution of 13.8 parts of sodium nitrite which is added rapidly with good stirring.

This solution can then be used for coupling, for example for the production of a product such as is mentioned in the table below.

- may be used for further reactions.

The structural formula of the-uncoupled prod- 'uct-is:-.. :1

O SOsNa OSOaNa Example 1 4 This is an example of the use of a body of indigoid type.

63 parts of the sodium-salt of 5:5'-dichlor 7 7-diamino-leuco-thio-indigodisulphuric ester (made by the action of a metal, pyridine and pyridine sulphuric anhydride on 5:5.-dichlor- 7 2 7'-di-acetyl-amino-thioindi o with subsequent alkali treatment) in solution in waterare acidified at O with 60 parts of concentrated hydrochloric acid and tetrazotized by the rapid addition of 13.8 parts of sodium nitrite in solution.

The clear dark brown solution contains the tetrazo body.

The structural formula ofthe product is:

OSOaNa Cl- C].

An example of a product obtained by coupling this will be found in the table below.

Example This is an example of the formation of an amino azo derivative.

A solution containingAZQ parts or the sodium salt of beta-aminQ-anthrahydrOquinQne-Q lO-di: sulphuric acid ester'made by alkaline hydrolysis of the corresponding-acetylamino ester, and therefore containing also in solution one molecular equivalent of sodium acetate, is neutralized with hydrochloric acidJ Thereafter parts of concentrated hydrochloric acidfare added. at 0 C. and thesolution-treated.with-3.45 parts of sodium nitrite in solution. i

The bright red color of the diazo compound gradually disappears and the solution acquires a bluish color. When all the diaz'o compound has disappeared, which takes'place after some hours stirring at room temperature, the beta-aminoalpha-- beta a'zo anthrahydroquinoneetetra-su1- phuric acid ester may be salted out or its solution The structural formula ,of the product is:-

OSOa Na N=N- OSOINB HzN osoiNa SOaNa Example 16 OS OaNa Ercample 17 This is a further example of the diazotization of an amino azo sulphuric acid ester.

58 parts of the amino azo body obtained by coupling diazotized paranitraniline with beta-aminoanthrahydroquinone disulphuric acid ester are dissolved in Water and diazotized at 0-5 C. by the addition of 30 parts of concentrated hydrochloric acid and 6.9 parts of sodium nitrite. The diazo compound separates out as a gelatinous red mass parts of 2% caustic soda.

" .5 purple in color.

The structural formula of the product is:

| N OSOINB u ,--N

osoava O O-lTIH The following table which is that referred to below, namely:--

soar! OaH above gives examples of some further dyestufis: where R is an aromatic residue.

bodiesof which the structural formulae are given ((1) Products having the following formula The invention is not limited to the above examples.

As regards the use of the coupled products, reference is made to our co-pending application re- The invention is of broad scope and includes limited to any theory which specifically among other bodies the series of V Color after Diazo compound Phenol or amine development Beta-diazo-anthrahydroquinone disulphuric acid ester... Ph n l Yellow Beta-diazo-anthrahydroquinone disulphuric acid ester Resorcinol Yellow Beta-diazo-anthrahydroquinone disulphuric acid ester.-- Betamaphthylamine. Yellow Beta-diazo-anthrahydroquinone disulphuric acid ester.-. Beta-hydroXy-naphthoic diaceto-acetic tolidide. Yellow Beta-diazo-anthrahydroquinone disulpliuric acid ester.-. .Beta hydroxy-naphthoic acid Red Beta-diazo-anthrahydroqninone disulphuric acid ester. 'Beta-hydroxy-naphthoic anilide Red Beta-diazo-anthraliydroquinone disulphuric acid ester. Dianisidide of beta-hydroxy-naphthoic acid. Red Beta-diazo-anthrahydroquinone disulphuric acid ester. Beta-hydroxy-naphthoic acid-alpha-naphthylid Red Beta-diazo-anthrahydroquinone disulphuric acid ester. Beta-hydroxynaphthoic acid beta-naphthylide. Red Beta-diazo-anthrahydroqninone disulphuric acid ester. Ortho-anisidide of beta hydroxy naphtlioic acid. Red Beta-diazo-anthrahydroqninone disulphuric-acid ester. Beta-hydroxy-naphthoic acid toluidide Red Beta-diazo-anthrahydroquinone disulphuric' acid ester. Para anisidide oibeta-hydroxy-naphthoic acid- Red Beta-diazo-anthrahydroquinone disulphuric acid ester. :5-dimethoxy-anilide'of beta-hydrcxy naphthoi Red 2-chlor-3 diazo-anthral1ydroquinone disulphuric acid ester.- fi-chlor-o-toluidlde of beta-hydroxy naphthoic acid Red 2-chlor-3-diazo-anthrahydroquincne disulpliuric acid ester.. Para-anisidide of beta-hydroxy-naphthoic acid- Red 2-chlor-3-diazo-antlnahydroquinone disulphuric acid ester... Beta-hydroxy-naphthoic anilide Red Color after Diazo compound Phenol development - 2-chlor-3-diazoanthrahydroquinone disulphuric acid ester.---. Betwhydroxy-naphthoic acid beta-naphthylide Red 2-clilor-3-diazo-anthrahydroquinone disulphnric acid ester. Ortho-anisidide of beta-hydroxy-naphthoic acid- Red 2-chlor-3'diazo-anthrahydroquinone disulphuric acid ester. Dianisidide of beta-hydroxy-naphthoic acid---.. Red 2-chlor-3-diazo-anthrahydrcquinone disulphuric acid ester Beta-hydroxy-naphthoic acid-alpha-naphthylide. Red 2-clilor-B-diazo-anthrahydroquinone (lisulphuric acid ester.. Beta-hydroxy-naphthoic acid tolnidide Red 2:6'tetrazo-anthrahydroqninone-Qzlo-disulphuric acid ester"-.. 5-chlor-o-toluidide of beta-hydroXy-naphthoic acid Red Alpl1a-diazo-anthrahydroquinone9:IO-disulphunc acid ester do Red 1-chlor-2-diazo-anthrahydroquinone-disulphuric acid ester do R d (0) Products having the following formula I (|)CH5 SIOaH a v -C) Having now described our invention, what we 7. Compounds which are chloro-derivatives of claim as new and desire to secure by Letters Patthe compound having the formu1aent is:-- r

1. The process which consists in diazotizing ,8 amino anthrahydroquinone -disulphuric-acidester with nitrous acid.

2. The process which consists in diazotizing p amino anthra hydro quinone-disulphuricacidester with sodium nitrite in the presence of '19 hydrochloric acid. 1 V A 35 3. The process which consists in, bringing to- 1 gether 2-amino-3-chlor-anthrahydroquinone-di- 50311 H sulphuric-acid-ester and a diazotizing agent. where R is an aromatic radical. 4. A process as claimed in claim 3 which con- 8. Compounds which are halogen-amino-sull5 sists in bringing together the resulting product phoor nitro-derivativesof the compounds hav- 90 and 'a'member of the group consisting of aroing the formulamatic amines and phenols. 801B 5. Products having the following formula:

H 0 0H GONE-R 10o whereR is an aromatic radical. V C1 9. Products which are 9-:10-disulphuric esters of 5-hydr0xynaphthoic acid arylide-azo-Z-anthrahydroquinones. 105

OzH ,7 V 10. B-diazoanthrahydroquinone disulphuric ester.

11. B-diazonium chloride of 'anthrahydroquinone disulphuric acid ester. no Where R an aromatic residue; 12. An azo dyestufi consisting of anthrahydroquinone disulphuric acid ester coupled through a produrctsn having h w formmazx diazo linkage in the fl-p'osition to an aromatic amine.

U a 13. An azo dyestufi consisting of anthrahydro- 40 7 I quinone disulphuric acid ester coupled through a 115 OCIhdiazo linkage in the p-position to an aromatic 5103B phenol. o 0H CONE-Q 14'. 2-diazo-3-chloranthrahydroquinone disule I phuric acid ester, N=N V 15. A proc'esswhich consists in diazotizing an 120 r anthrahydroquinone disulphuric ester containng' 01 i a diazoizable amino group. DAVID ALEXANDER WHYTE 0 v FAIRWEATHER. n J. THOMAS. 125

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